the effect of high-energy ionizing radiation on the
TRANSCRIPT
materials
Article
The Effect of High-Energy Ionizing Radiation on theMechanical Properties of a Melamine Resin,Phenol-Formaldehyde Resin, and NitrileRubber Blend
Ivan Kopal 1,*, Juliana Vršková 1, Ivan Labaj 1, Darina Ondrušová 1, Peter Hybler 2,Marta Harnicárová 3,4, Jan Valícek 3,4 and Milena Kušnerová 4
1 Faculty of Industrial Technologies in Púchov, Alexander Dubcek University of Trencín, Ivana Krasku 491/30,020 01 Puchov, Slovakia; [email protected] (J.V.); [email protected] (I.L.);[email protected] (D.O.)
2 Progresa Final SK, s.r.o., Feriencíková 18, 811 08 Bratislava, Slovakia; [email protected] Faculty of Engineering, Slovak University of Agriculture in Nitra, Tr. A. Hlinku 2, 949 76 Nitra, Slovakia;
[email protected] or [email protected] (M.H.); [email protected] [email protected] (J.V.)
4 Institute of Technology and Business in Ceské Budejovice, Faculty of Technology, Department of MechanicalEngineering, Okružní 10, 370 01 Ceské Budejovice, Czech Republic; [email protected]
* Correspondence: [email protected]; Tel.: +421-42-2851-826
Received: 25 October 2018; Accepted: 26 November 2018; Published: 28 November 2018 �����������������
Abstract: Irradiation by ionizing radiation is a specific type of controllable modification of thephysical and chemical properties of a wide range of polymers, which is, in comparison to traditionalchemical methods, rapid, non-polluting, simple, and relatively cheap. In the presented paper,the influence of high-energy ionizing radiation on the basic mechanical properties of the melamineresin, phenol-formaldehyde resin, and nitrile rubber blend has been studied for the first time.The mechanical properties of irradiated samples were compared to those of non-irradiated materials.It was found that radiation doses up to 150 kGy improved the mechanical properties of the testedmaterials in terms of a significant increase in stress at break, tensile strength, and tensile modulusat 40% strain, while decreasing the value of strain at break. At radiation doses above 150 kGy,the irradiated polymer blend is already degrading, and its tensile characteristics significantlydeteriorate. An radiation dose of 150 kGy thus appears to be optimal from the viewpoint of achievingsignificant improvement, and the radiation treatment of the given polymeric blend by a beam ofaccelerated electrons is a very promising alternative to the traditional chemical mode of treatmentwhich impacts the environment.
Keywords: high-energy ionizing radiation; polymer modification; mechanical properties;polymer blends; polymer friction composite systems
1. Introduction
The modification of construction materials, including polymers, is inevitable, particularlyin order to achieve properties meeting all the requirements of increasingly-demanding practicalapplications [1]. At present, a way to tailor the properties of polymeric materials in industrialpractice is their treatment with ionizing beta radiation generated in electron accelerators, which arecapable of producing high radiation doses in a relatively very short time. High-energy ionizingradiation can modify the macroscopic properties and molecular structure of the irradiated polymers [2].
Materials 2018, 11, 2405; doi:10.3390/ma11122405 www.mdpi.com/journal/materials
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During electron beam irradiation (EB), the energy of accelerated electrons is injected directly into amaterial, in which it subsequently induces chemical reactions, often without the need for any catalyst.The processes initiated by EB radiation in the polymer are very complex, as they are accompanied byseveral simultaneously running, competitive reactions, such as cross-linking, degradation, oxidation,fragmentation, grafting, and others [3]. However, the most useful reaction occurring during polymerirradiation is a radiation-induced cross-linking of polymer chains, which is capable of improvingsome physical and chemical properties, such as hardness, resilience, thermal resistance, solubility,and several others [4]. For a relatively large group of polymers modified by high energy EBradiation, the improvement of these properties is even more substantially pronounced than thatachievable by conventional cross-linking [5]. In general, EB radiation causes the excitation of polymericmacromolecules occurring adjacent to the incident electrons. The energies associated with the excitationof these molecules are proportional to the electron velocities and the radiation dose [6]. The interactionof incident electrons with molecules leads to ionization in the polymer and numerous highly-reactiveforms are produced (such as free neutral radicals, radical cations and anions, low energy electrons,and singlet and triplet states of molecules excited by electrons) in a whole series of processes (suchas fragmentation to carbocations and free radicals, capture of electrons by polymeric and oxygenmolecules, dissociative capture of electrons, and others) [7]. Free radicals formed by dissociationof the molecules in their excited state or by the interaction of molecular ions, as well as molecularions, can react by linking the polymer chains directly to the 3D network structure or by initiatinggrafting reactions. Due to the full depth of penetration of the incident electrons, EB radiation resultsin uniformly-cured polymers [8]. Chain branching and cross-linking increase the molecular weightof the polymer, while degradation or scission causes a reduction of the initial molecular weight.During irradiation, both these phenomena coexist, and their prevalence depends on several factors,such as the initial molecular structure and morphology of the polymer, and the radiation conditions.The EB radiation-induced cross-linking will result in an increase in physical and chemical propertiesuntil chain scission and breaking of intermolecular bonds reduces them; therefore, finding an optimalradiation dose is always necessary in order to prevent polymer degradation caused by excessiveirradiation [8,9].
At present, a number of research papers are dedicated to the modification of polymers by EBradiation. The fundamental principles of all applications of radiation treatment of polymers areevaluated, for example, in [10]. In general, it is well known that some polymers can be cross-linkedwith EB radiation, while others tend to degrade. Some of them are capable of self-cross-linking,while some have to be first mixed with a cross-linking agent, and EB modification is applied onlyduring their polymerization process, which is presented in a number of cases in [11]. Ref. [12] givesa brief overview of polymers modifiable and non-modifiable by ionizing radiation. The aim of thepaper [13] is to balance the applications of radiation cross-linking of polymers in chemically-aggressiveand high-temperature conditions. Ref. [14] studies the mechanical and thermal properties of the epoxyresin irradiated by EB irradiation with doses up to 300 kGy; its authors deal with the process of curingwith EB irradiation, using cationic initiators of the cross-linking reaction. The result of radiation curingis compared with the result of the process of heat curing that is used in a standard manner for thistype of polymers. The samples of the investigated material were irradiated by EB irradiation forseveral minutes with a total dose of 150 kGy. The heat curing process was carried out for 20 h intotal. The glass transition temperatures, Tg, determined by the DMA (dynamic mechanical analysis)technology, achieved values higher even by 17 per cent in irradiated samples compared to heat-curedsamples, due to the higher density of the formed polymeric 3D network resulting in higher stiffnessof the material cured by irradiation. The authors of this paper concluded that curing of epoxy resinby EB irradiation may be particularly suitable for applications in which high thermal stability andheat resistance are required. Ref. [15] deals with the study of the thermal and mechanical properties ofepoxy-diane resin cured with polyethylene-polyamine after irradiation by doses of 30, 100, and 300 kGy.The effects of individual radiation doses were investigated using standard static tensile tests, as well
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as with the use of TGA (thermogravimetric analysis) and DMA methods. It was found that thethermal properties of the investigated material slightly increased after EB irradiation. Mechanicalproperties increased after irradiation by doses of 30 kGy and 100 kGy, while at a dose of 300 kGy,they significantly decreased. The impact of EB irradiation on the mechanical and dynamic mechanicalproperties of cross-linked fluorocarbon rubber, natural rubber, ethylene-propylene-diene monomer ofrubber, and nitrile rubber was investigated [16]. It was found that the modulus of elasticity, gel portion,the temperature of glass transition, and dynamic elastic modulus of the investigated vulcanizatesincrease with the increasing irradiation dose, while the elongation at break and the loss factor decrease.The authors of the paper [17] studied the mechanism of interaction between carbon fibers and phenolepoxy matrixes of polymeric composites cured by EB radiation, as well as improving their interfacialshear strength. Promising results were obtained by electrochemical processing of carbon fibersfollowed by subsequent application of a reagent compatible with the applied EB. The morphology ofboth modified and unmodified carbon fibers was characterized by the use of SEM (scanning electronmicroscopy), AFM (atomic force microscopy), and XPS (X-ray photoelectron spectroscopy). It wasproved that acidic electrolytes are particularly well-suited to improving interfacial adhesion in the EBcuring process. Alkaline groups on carbon fibers prevent cationic polymerization and improve theshear strength of EB-cured composites.
The majority of relevant papers publish the results of research on the impact of high-energyEB irradiation on the micromechanical, thermo-mechanical, visco-elastic, and rheological propertiesof various types of polymeric materials, their mixtures and composites, nanocomposites based onpolymeric matrixes, as well as the influence of irradiation on changes in their structure, degree ofcross-linking, crystallinity, and gel content under various conditions of radiation exposure, typicallyup to 300 kGy, using the most advanced analytical tools for modern, standard mechanical tests: TGA,DMA, and DSC (differential scanning calorimetry) techniques, FT-IR (Fourier-transform infraredspectroscopy) and Raman spectroscopy, SEM, AFM, or XPS. However, to the best of our knowledge,no previous studies have been reported describing the effect of EB irradiation on the polymer blend ofmelamine resin, phenol-formaldehyde resin, and nitrile rubber, representing a specific three-componentmixture of two reactoplastics and one elastomer, as well as its individual components. The modelsof the results of an interaction of ionizing radiation with polymeric systems are virtually completelymissing. For this reason, the aim of the present paper is to investigate and model the influence ofEB irradiation on the mechanical properties of the aforementioned polymeric composition whichare commonly used as a polymeric matrix of friction composite systems in a number of practicalapplications, particularly in the automotive industry [18].
2. Materials and Methods
2.1. Preparation of Samples
The PMX3 polymer system (PS) was purchased from a professional material manufacturer forpolymer matrices of friction composite systems [19]. PS PMX3 consists of a mixture of melamine resin,phenol-formaldehyde resin, and nitrile rubber, which is distributed by the manufacturer (Ahshenhui,Jinhu, China) in the form of granules as a polymer blend with a proportion of ingredients adapted forwider use in the automotive industry. PS PMX3 was plasticized for 15 min at 110 ± 2 ◦C and pressure(80 ± 1) kN in a Fontijne Presses vulcanization press, LabEcon Series 600 (Fontijne, Barendrecht,The Netherlands), followed by homogenization using a laboratory double roller VOGT LaboWalz W 80T (VOGT, Berlin, Germany) into plates of thickness (2 ± 0.05) mm. Prior to further processing, PS PMX3was allowed to stand for 24 h at 25 ± 2 ◦C. Pieces in the shape of a two-sided blade in accordance withstandard ISO 37 [20] or ASTM D 412 [21], were cut out from the prepared plates by a pneumatic cutterCEAST, Hollow Punch-pneumatic 6054.000 (Instron, Bucking-Hamshire, UK). The dimensions of thetest pieces (Type 2) were as follows: overall length (minimum)—75 mm, width of ends—(25 ± 1) mm,
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length of narrow portion—(25 ± 1) mm, width of narrow portion—(4 ± 0.1) mm, transition radiusoutside—(8 ± 0.5) mm, transition radius inside—(12.5 ± 1) mm.
2.2. Radiation Treatment
Irradiation of the samples was carried out using a linear electron accelerator UELR-5-1S (NIIEFA,Sankt-Peterburg, Russia) with a vertical design of the construction. The source of electrons in theaccelerator is an indirectly-heated, pressed Ba-Ni cathode with a diameter of 5 mm. The emittedelectrons are formed by the electron-optical system designed by J.R. Pierce. The increase in thekinetic energy of the electrons is ensured by the electric field of the stationary electromagnetic waveproduced by a magnetron operating in the pulse mode at a frequency of 2998 MHz. The focusing ofthe beam is realized by the high-frequency field. The output device (scanning chamber) provides theebeam with a band of lengths 400 mm, 450 mm and 500 mm. The beam outlet to the atmosphere isthrough 50 µm thick titanium foil. The dispatch of the beam is realized in a vacuum chamber by ascanning electromagnet.
The technical parameters of the accelerator during the experiments were the following: the energyof electrons (5 ± 5%) MeV, pulse duration (3.5 ± 0.5) µs, beam diameter at the outlet of the foil≥2 mm. Homogeneous irradiation of the samples of the investigated PS PMX3 was ensured in adynamic manner, i.e., that the irradiated samples were uniformly moving on the conveyor under thebeam at a defined velocity. The experiments were carried out in the air, at normal pressure, and atroom temperature. Excessive overheating due to higher doses of irradiation was prevented by theplacement of the samples on heat-insulating materials and by air flowing from the ventilation system.The ventilation system also provided an extraction of the ozone generated during irradiation.
The samples were irradiated with a wide span of target doses, namely: 77, 138, 150, 180, 190,and 284 kGy. The doses above 150 kGy, which were above the maximum limit of dosimetric systems,were executed by multiple irradiations. The break between two exposures did not exceed 20 min.The total irradiation time of the samples at individual radiation doses did not exceed 54 min. Due tothe required high radiation doses, the highest accelerator outputs corresponding to pulse frequencies ofebeam the 120 Hz and 240 Hz bands were used. The dose depends on the speed of the conveyor sectionbelow the accelerator window, and this dependence is non-linear and is determined experimentally.Calculation of radiation doses was performed by a routine dosimetric system using radiochromicB3 foils (GEX Corporation, Centennial, CO, USA). The foils cut to circles with a diameter of 1 cmreact to radiation by showing a change of color. The absorption coefficients of the irradiated foilswere measured by spectrophotometer (Genesys20, Thermo Electron Corporation, Madison, WI, USA).The radiation dose is calculated from the experimentally-determined dependencies of the dose onabsorbance. The combined uncertainty of the applied dosimetric system is ≤6%.
2.3. Static Uniaxial Tensile Tests
The tensile properties of the samples of the investigated material were determined using acomputer-controlled universal tensile tester Shimadzu AG-X Plus shifter (Shimadzu, Tokyo, Japan)with two pneumatic clamping jaws with a mutual movement speed of (100 ± 5) mm·min−1 at roomtemperature. The mean value of at least five dumbbell specimens of each sample, prepared inaccordance with standards ISO 37 or ASTM D 412 [20,21], was taken, although specimens that broke inan unusual manner were disregarded. The average engineering stress-strain curves were constructedfrom the obtained experimental average force vs. elongation data with a maximum relative standarddeviation of 5%, and they were analyzed using the software package Matlab® Version 7.10.0.499R2010a 64-bit (MathWorks, Natick, MA, USA).
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3. Results and Discussion
3.1. Changes in Mechanical Properties
The results of the uniaxial tensile tests for samples of the non-irradiated PS PMX3 and PS PMX3irradiated with high energy EB radiation by doses ranging from 77 kGy to 284 kGy, in the form ofaverage engineering stress-strain curves, are presented in Figure 1a. As expected, the effect of EBirradiation on the shape of the stress-strain curves, obtained under the given conditions of tensile tests,is evident. It is apparent already at a first glance that all curves exhibit a relatively short linear elasticregion with a low proportionality ratio, a relatively short linear visco-elastic region with low value oflimit of elasticity, a relatively low value of tensile modulus and ultimate strength, as well as tear stress,but that their strain at break achieves an extremely wide range of values. A detailed view of the linearregion of the stress-strain curves is shown in Figure 1b.
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average engineering stress-strain curves, are presented in Figure 1a. As expected, the effect of EB
irradiation on the shape of the stress-strain curves, obtained under the given conditions of tensile
tests, is evident. It is apparent already at a first glance that all curves exhibit a relatively short linear
elastic region with a low proportionality ratio, a relatively short linear visco-elastic region with low
value of limit of elasticity, a relatively low value of tensile modulus and ultimate strength, as well as
tear stress, but that their strain at break achieves an extremely wide range of values. A detailed view
of the linear region of the stress-strain curves is shown in Figure 1b.
(a) (b)
Figure 1. (a) Experimental average engineering stress-strain curves of non-irradiated polymeric
system PMX3 and of polymeric system PMX3 modified by various radiation doses of ionizing EB
radiation; (b) Detailed representation of the linear region of the stress-strain curves.
The shape of the stress-strain curve of the virgin sample resembles the stress-strain curve of the
linear amorphous reactoplastics (non-cross-linked resins) with low strength, without an ultimate
strength, but with ductility of non-cross-linked, non-crystallizing elastomers in a rubbery state near
viscous flow temperature [22]. Once the strength limit has been reached, the stress decreases with
the increasing strain in a non-linear manner, albeit continuously. The material ductility at the same
time was so big that its sample during the performed tensile tests could not be ruptured even at a
strain above 500%. The stress-strain curves after irradiation of material with radiation doses of 77
kGy and 138 kGy show the characteristics of partially cross-linked non-crystallising elastomers in a
rubbery state high above the temperature of their glass transition Tg [23], with much higher strength
and lower ductility than in the non-irradiated sample.
As a result of irradiation of the sample with a radiation dose of 150 kGy, its stress-strain curve
showed a shape corresponding to the tensile response of a brittle, three-dimensional (already cured)
amorphous resin in a glassy state, well below the Tg temperature [24], with ductility smaller than in
the case of application of lower radiation doses. The strength of the irradiated material at a dose of
150 kGy achieves the maximum value at the same time. The shape of the stress-strain curve at higher
radiation doses corresponds to curves of the amorphous cured resins in a glassy state, at a
temperature just below Tg [22], with strength substantially lower than at a dose of 150 kGy, and with
a corresponding ductility.
It is evident from the above that the tensile response of the virgin sample reflects the mechanical
properties of the polymeric blend of non-cross-linked resins and rubber forming PS PMX3. After
irradiation with radiation doses below 150 kGy, the mechanical properties of the partially
cross-linked rubber predominate. At a dose of 150 kGy, the properties of the cured resins are
dominant, whereas, at higher radiation doses, the effects of radiation-induced degradation of a
polymeric network of irradiated material are manifested with predominant mechanical properties of
the cured resins. During EB irradiation with radiation doses within the given range of values, the
irradiated material progressively enters various physical states undergoing various relaxation
transitions events initiated by the absorbed ionizing radiation, resulting in observed non-linear
Figure 1. (a) Experimental average engineering stress-strain curves of non-irradiated polymeric systemPMX3 and of polymeric system PMX3 modified by various radiation doses of ionizing EB radiation;(b) Detailed representation of the linear region of the stress-strain curves.
The shape of the stress-strain curve of the virgin sample resembles the stress-strain curve ofthe linear amorphous reactoplastics (non-cross-linked resins) with low strength, without an ultimatestrength, but with ductility of non-cross-linked, non-crystallizing elastomers in a rubbery state nearviscous flow temperature [22]. Once the strength limit has been reached, the stress decreases with theincreasing strain in a non-linear manner, albeit continuously. The material ductility at the same timewas so big that its sample during the performed tensile tests could not be ruptured even at a strainabove 500%. The stress-strain curves after irradiation of material with radiation doses of 77 kGy and138 kGy show the characteristics of partially cross-linked non-crystallising elastomers in a rubberystate high above the temperature of their glass transition Tg [23], with much higher strength and lowerductility than in the non-irradiated sample.
As a result of irradiation of the sample with a radiation dose of 150 kGy, its stress-strain curveshowed a shape corresponding to the tensile response of a brittle, three-dimensional (already cured)amorphous resin in a glassy state, well below the Tg temperature [24], with ductility smaller thanin the case of application of lower radiation doses. The strength of the irradiated material at a doseof 150 kGy achieves the maximum value at the same time. The shape of the stress-strain curve athigher radiation doses corresponds to curves of the amorphous cured resins in a glassy state, at atemperature just below Tg [22], with strength substantially lower than at a dose of 150 kGy, and with acorresponding ductility.
It is evident from the above that the tensile response of the virgin sample reflects themechanical properties of the polymeric blend of non-cross-linked resins and rubber forming PS
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PMX3. After irradiation with radiation doses below 150 kGy, the mechanical properties of thepartially cross-linked rubber predominate. At a dose of 150 kGy, the properties of the cured resinsare dominant, whereas, at higher radiation doses, the effects of radiation-induced degradation of apolymeric network of irradiated material are manifested with predominant mechanical propertiesof the cured resins. During EB irradiation with radiation doses within the given range of values,the irradiated material progressively enters various physical states undergoing various relaxationtransitions events initiated by the absorbed ionizing radiation, resulting in observed non-linear changesin its mechanical properties. A more detailed analysis of the stress-strain curves makes it possible toquantify the effect of the magnitude of radiation dose on the basic mechanical characteristics of theinvestigated PS PMX3, such as stress and strain at break, ultimate limit, and the tensile modulus M 40.The tensile modulus at 40% strain was selected for assessing the stiffness of the irradiated material inthe initial stages of deformation mainly because of the possibility of its identification for all appliedradiation doses to the break of the sample and a good information capability on the elasticity of testedmaterial [23].
The values of strain at break εb and of the tensile stress at break σb of the investigated PS PMX3 fordifferent radiation doses, in the form of stress-strain curves to the break of the sample, are presentedin Figure 2a, while their changes with the increasing dose of irradiation are shown in Figure 2b.Vertical abscissas show the error intervals of experimental data with the corresponding standarddeviation. It is evident from Figure 2a,b that up to a dose of 150 kGy, εb decreases in a non-linearmanner, but continuously, with a corresponding increase of σb. Changes in values εb and σb afterirradiation of the samples of PS PMX3 by radiation doses of 77 kGy, 138 kGy, and 150 kGy thusshow the expected opposite trend. The value εb = 180.9% at 150 kGy versus the value εb = 332.4%at a dose of 138 kGy is approximately 1.84 times lower, and compared to the value εb = 426% at77 kGy, it is approximately 2.36 times lower. The value σb = 7.681 MPa at 150 kGy is versus the valueσb = 4.441 MPa at 138 kGy more than 1.73 times higher, and compared to the value σb = 2.466 MPa at77 kGy, it is approximately 3.12 times higher. The identified changes of values εb and σb demonstratethe changes in the mechanical properties of the irradiated PS PMX3 in this interval of radiationdoses in terms of a significant reduction in its total ductility (εb), while at the same time, its tensilestrength (σb) significantly increases due to the prevalence of cross-linking reactions over the intensityof the reactions of polymer chain scission and degradation of intermolecular cross-links initiatedby the absorbed high-energy EB radiation [25]. Higher radiation doses produce more cross-linksbetween macromolecular chains of irradiated material, resulting in an increase in resistance to therelease of intermolecular forces by mechanical loading, or in an increase in its stiffness. At higherradiation doses, the polymeric network becomes tighter, and it restricts the internal mobility ofthe chains, thereby increasing the resistance of the irradiated material to its mechanical damage,or its strength [26]. Higher density of 3D structures of polymeric network and limited mobility ofpolymeric chains, i.e., higher stiffness, as well as strength of material due to irradiation by higherradiation doses, also prevent the structural reorganization of polymeric chains during its tensile stress,which significantly reduces the ability of PS PMX3 to be plastically deformed by drawing, or itsductility [27]. At radiation doses above 150 kGy, the dependence of both εb and σb on the magnitudeof the dose of the absorbed EB radiation is non-monotonic. At 180 kGy σb, it drops to the value of6.637 MPa, while εb rises to 281.2%; at 190 kGy, σb and εb simultaneously drop to 3.172 MPa and54.39%, while at a dose of 284 kGy, σb and εb simultaneously increase to the values of 5.041 MPaand 107.5%, respectively. At a dose of 180 kGy, due to the dominance of the degradation processesover the radiation, cross-linking prevails over the degradation of transverse inter-molecular bondsbetween the chains of the polymeric network over their production, which makes the network lesstight. The lower density of bonds reduces the size of intermolecular interactions and releases limitedmobility of chains, which is accompanied by observed decreases in strength (σb) and increased ductility(εb) of the irradiated material. During further increases of the radiation dose, the changes of εb and σbshow the same trend with an analogous course, so it is possible to assume that further degradation of
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the radiation-induced polymeric network of the irradiated material will occur. The εb and σb values forthe non-irradiated sample could not be determined, as it was not ruptured under the given conditionsof the tensile tests.
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kGy, σm = 4.734 MPa at 138 kGy and σm = 7.674 MPa at 150 kGy, compared to the non-irradiated
sample σm = 2.143 MPa, are approximately 1.5, 2.1, and 3.6 times higher, respectively. Values of the
modulus M 40 = 2.598 MPa at 77 kGy, M 40 = 3.059 MPa at 138 kGy and M 40 = 4.3110 MPa at 150
kGy, compared to M 40 = 2.13 MPa for a non-irradiated sample, are approximately 1.2, 1.4, and 2
times higher, respectively. The recorded changes in the values of σm and M 40 after application of
radiation doses of 77 kGy, 138 kGy, and 150 kGy demonstrate the expected increase in tensile
strength of the irradiated PS PMX3 with a simultaneous increase in stiffness at the initial stages of
deformation, which can also be attributed to the prevailing radiation-induced cross-linking reactions
over the degradation processes in the irradiated material, with the mechanism described above. At
radiation doses above 150 kGy, as with at εb and σb, the dependencies of both σm and M 40 on the
magnitude of the dose of the absorbed radiation are non-monotonic, but they exhibit the same trend
with an analogous course. At 180 kGy, the value σm drops to 6.682 MPa and M 40 drops to 3.67 MPa;
at 190 kGy, the value σm drops to 3.476 and M 40 drops to 3.21 MPa, due to the induction-induced
reduction of strength and an increase of the ductility of the sample due to the predominance of the
degradation processes over the forming processes of the polymer network with the mechanism
described above. At a dose of 284 kGy, the values of σm and M 40 simultaneously increase to 5.551
MPa and 3.931 MPa, respectively. However, this increase in σm and M 40, as well as the increase of εb
and σb at the radiation dose of 284 kGy, is due to the continued degradation of the sample material,
and not to the subsequent process of formation of the polymeric network or by the
radiation-induced change of crystallinity of PS PMX3 [28]. Due to the chemical composition of the
irradiated material, it can be assumed that at high radiation doses, the cross-linked nitrile rubber
therein becomes completely disintegrated, and it thereby transforms to a filler dispersed in the
polymeric matrix of the blend of melamine and phenol-formaldehyde resin of the composite created
by the high-energy EB irradiation with mechanical properties quite different from those of the
original polymer system. However, this assumption will need to be verified in ongoing research
using the DSC, DMTA, TGA, and FT-IR techniques, or other diagnostic techniques.
(a) (b)
Figure 2. (a) Presentation of the values of strain at the break εb and of stress at break σb of the
polymeric system PMX4 for various radiation doses; (b) The effect of the radiation dose on the values
of strain at break εb and stress at break σb of the polymeric system PMX3.
The ultimate strength after irradiation of the investigated material with a radiation dose of 150
kGy is equal to the stress at break of σb, which is typical for brittle amorphous polymers, such as
cross-linked reactoplasts, including the cured resins [24]. During all other applied radiation doses,
the tensile response of the irradiated PS exhibits signs of the tensile response of more ductile
materials with significantly lower stiffness and strength [23]. From the point of view of enhancement
of mechanical properties of the investigated PS PMX3 with its irradiation by high-energy EB
radiation, it is possible to consider the radiation dose of 150 kGy as optimal.
Figure 2. (a) Presentation of the values of strain at the break εb and of stress at break σb of the polymericsystem PMX4 for various radiation doses; (b) The effect of the radiation dose on the values of strain atbreak εb and stress at break σb of the polymeric system PMX3.
The values of the strength limit σm and the modulus M 40 of the investigated PS PMX3 for thevirgin sample and the samples irradiated with different doses of EB radiation are presented in Figure 3a,and their changes with the increasing dose of absorbed radiation are shown in Figure 3b. For clarity,Figure 3a shows the entire stress-strain curves till completion of the tensile tests, not only after theyhave been torn apart, as in Figure 2a. It is evident from Figure 3a,b that up to a dose of 150 kGyboth σm and M 40 are non-linear, but they grow monotonously. The values σm = 3.23 MPa at 77 kGy,σm = 4.734 MPa at 138 kGy and σm = 7.674 MPa at 150 kGy, compared to the non-irradiated sampleσm = 2.143 MPa, are approximately 1.5, 2.1, and 3.6 times higher, respectively. Values of the modulusM 40 = 2.598 MPa at 77 kGy, M 40 = 3.059 MPa at 138 kGy and M 40 = 4.3110 MPa at 150 kGy, comparedto M 40 = 2.13 MPa for a non-irradiated sample, are approximately 1.2, 1.4, and 2 times higher,respectively. The recorded changes in the values of σm and M 40 after application of radiation doses of77 kGy, 138 kGy, and 150 kGy demonstrate the expected increase in tensile strength of the irradiatedPS PMX3 with a simultaneous increase in stiffness at the initial stages of deformation, which canalso be attributed to the prevailing radiation-induced cross-linking reactions over the degradationprocesses in the irradiated material, with the mechanism described above. At radiation doses above150 kGy, as with at εb and σb, the dependencies of both σm and M 40 on the magnitude of the dose ofthe absorbed radiation are non-monotonic, but they exhibit the same trend with an analogous course.At 180 kGy, the value σm drops to 6.682 MPa and M 40 drops to 3.67 MPa; at 190 kGy, the value σm
drops to 3.476 and M 40 drops to 3.21 MPa, due to the induction-induced reduction of strength and anincrease of the ductility of the sample due to the predominance of the degradation processes over theforming processes of the polymer network with the mechanism described above. At a dose of 284 kGy,the values of σm and M 40 simultaneously increase to 5.551 MPa and 3.931 MPa, respectively. However,this increase in σm and M 40, as well as the increase of εb and σb at the radiation dose of 284 kGy, is dueto the continued degradation of the sample material, and not to the subsequent process of formation ofthe polymeric network or by the radiation-induced change of crystallinity of PS PMX3 [28]. Due tothe chemical composition of the irradiated material, it can be assumed that at high radiation doses,the cross-linked nitrile rubber therein becomes completely disintegrated, and it thereby transforms to afiller dispersed in the polymeric matrix of the blend of melamine and phenol-formaldehyde resin of thecomposite created by the high-energy EB irradiation with mechanical properties quite different from
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those of the original polymer system. However, this assumption will need to be verified in ongoingresearch using the DSC, DMTA, TGA, and FT-IR techniques, or other diagnostic techniques.Materials 2018, 11, x FOR PEER REVIEW 8 of 13
(a) (b)
Figure 3. (a) Presentation of the strength limit values σm and the modulus M 40 of the polymeric
system PMX3 for the virgin sample and for the samples irradiated with different radiation doses; (b)
Effect of the radiation dose on the strength limit values σm and the modulus M 40 of the polymeric
system PMX3.
The experimental values of the monitored mechanical characteristics for the virgin sample, as
well as for the PS PMX3 samples irradiated with the individual radiation doses, are summarized in
Table 1
Table 1. Experimental values of mechanical characteristics εb, σb, σm and M 40 for the virgin sample
of PMX3 polymer system and samples irradiated with individual radiation doses.
Mechanical Characteristics 0 kGy 77 kGy 138 kGy 150 kGy 180 kGy 190 kGy 284 kGy
εb (%) - 426.1 332.4 180.9 281.2 54.4 107.5
σb (MPa) - 2.466 4.441 7.681 6.637 3.172 5.041
σm (MPa) 2.143 3.234 4.734 7.674 6.682 3.476 5.551
M 40 (MPa) 2.132 2.598 3.059 4.311 3.672 3.213 3.931
3.2. Regression Analysis
The effect of EB irradiation on the change of mechanical properties of PS PMX3 by radiation
doses up to 150 kGy, at which it is possible to observe a significant improvement, is demonstrated by
results of the regression analysis at the confidence level of 95% shown in Figure 4a,b (for εb and σb),
and in Figure 5a,b (for σm and M 40).
(a) (b)
Figure 4. (a) Regression analysis of the functional dependence of strain at break εb on the radiation
dose; (b) Regression analysis of the functional dependence of stress at break σb on the radiation dose.
Figure 3. (a) Presentation of the strength limit values σm and the modulus M 40 of the polymericsystem PMX3 for the virgin sample and for the samples irradiated with different radiation doses;(b) Effect of the radiation dose on the strength limit values σm and the modulus M 40 of the polymericsystem PMX3.
The ultimate strength after irradiation of the investigated material with a radiation dose of 150 kGyis equal to the stress at break of σb, which is typical for brittle amorphous polymers, such as cross-linkedreactoplasts, including the cured resins [24]. During all other applied radiation doses, the tensileresponse of the irradiated PS exhibits signs of the tensile response of more ductile materials withsignificantly lower stiffness and strength [23]. From the point of view of enhancement of mechanicalproperties of the investigated PS PMX3 with its irradiation by high-energy EB radiation, it is possibleto consider the radiation dose of 150 kGy as optimal.
The experimental values of the monitored mechanical characteristics for the virgin sample, as wellas for the PS PMX3 samples irradiated with the individual radiation doses, are summarized in Table 1.
Table 1. Experimental values of mechanical characteristics εb, σb, σm and M 40 for the virgin sample ofPMX3 polymer system and samples irradiated with individual radiation doses.
Mechanical Characteristics 0 kGy 77 kGy 138 kGy 150 kGy 180 kGy 190 kGy 284 kGy
εb (%) - 426.1 332.4 180.9 281.2 54.4 107.5σb (MPa) - 2.466 4.441 7.681 6.637 3.172 5.041σm (MPa) 2.143 3.234 4.734 7.674 6.682 3.476 5.551
M 40 (MPa) 2.132 2.598 3.059 4.311 3.672 3.213 3.931
3.2. Regression Analysis
The effect of EB irradiation on the change of mechanical properties of PS PMX3 by radiation dosesup to 150 kGy, at which it is possible to observe a significant improvement, is demonstrated by resultsof the regression analysis at the confidence level of 95% shown in Figure 4a,b (for εb and σb), and inFigure 5a,b (for σm and M 40).
Materials 2018, 11, 2405 9 of 13
Materials 2018, 11, x FOR PEER REVIEW 8 of 13
(a) (b)
Figure 3. (a) Presentation of the strength limit values σm and the modulus M 40 of the polymeric
system PMX3 for the virgin sample and for the samples irradiated with different radiation doses; (b)
Effect of the radiation dose on the strength limit values σm and the modulus M 40 of the polymeric
system PMX3.
The experimental values of the monitored mechanical characteristics for the virgin sample, as
well as for the PS PMX3 samples irradiated with the individual radiation doses, are summarized in
Table 1
Table 1. Experimental values of mechanical characteristics εb, σb, σm and M 40 for the virgin sample
of PMX3 polymer system and samples irradiated with individual radiation doses.
Mechanical Characteristics 0 kGy 77 kGy 138 kGy 150 kGy 180 kGy 190 kGy 284 kGy
εb (%) - 426.1 332.4 180.9 281.2 54.4 107.5
σb (MPa) - 2.466 4.441 7.681 6.637 3.172 5.041
σm (MPa) 2.143 3.234 4.734 7.674 6.682 3.476 5.551
M 40 (MPa) 2.132 2.598 3.059 4.311 3.672 3.213 3.931
3.2. Regression Analysis
The effect of EB irradiation on the change of mechanical properties of PS PMX3 by radiation
doses up to 150 kGy, at which it is possible to observe a significant improvement, is demonstrated by
results of the regression analysis at the confidence level of 95% shown in Figure 4a,b (for εb and σb),
and in Figure 5a,b (for σm and M 40).
(a) (b)
Figure 4. (a) Regression analysis of the functional dependence of strain at break εb on the radiation
dose; (b) Regression analysis of the functional dependence of stress at break σb on the radiation dose.
Figure 4. (a) Regression analysis of the functional dependence of strain at break εb on the radiationdose; (b) Regression analysis of the functional dependence of stress at break σb on the radiation dose.Materials 2018, 11, x FOR PEER REVIEW 9 of 13
(a) (b)
Figure 5. (a) Regression analysis of the functional dependence of the strength limit σm on the
radiation dose; (b) Regression analysis of the functional dependence of the modulus M 40 on the
radiation dose.
The realized regression analysis of the experimental data has shown that all the analyzed
functional dependencies at a given interval of radiation dose can be described with a relatively high
degree of reliability by a single regression model, in the form
( )1
Δ exp ,imN
iii
xy x y δ
θ=
= +
(1)
where y(x) is the corresponding mechanical characteristic of the irradiated material, x is the radiation
dose absorbed, and Δyi, θi, mi, and δ represent unknown but the correct coefficients of the model that
have been reliably estimated in the process of parametric fitting of experimental data using the Trust
Region algorithm of non-linear least squares method [29] in the device ‘CF Tool’ of the Matlab®
software package. The following is then valid for the model coefficients Δyi:
( )1
Δ 0 ,N
ii
y y δ=
= − (2)
where y(0) is the initial value of the corresponding mechanical characteristic as it follows from the
relation (1) for x = 0. The subscript i pertains to critical points of the curve y = y (x) where a significant
change in the velocity of its trend takes place, and N is the number of these critical points. The
negative value of the quotient in the model exponent then represents a decreasing trend, while its
positive value represents the increasing trend of y(x). The coefficient δ represents a non-constant
error parameter of the model, which will be discussed later.
The dashed lines in Figures 4 and 5 represent the 95% prediction intervals of the estimated
coefficients of the model representing the 5% probability that the results of future measurements of
the mechanical characteristics of the irradiated PS PMX3 under the same experimental conditions
will not lie between their lower and upper boundaries [30].
The regression model (1) describes changes in the observed mechanical characteristics of the
irradiated polymeric material due to the prevalence of formation of transverse intermolecular bonds
between macromolecular chains and their simultaneous breaking accompanied by degradation of
the formed polymer network. Due to the different nature of intermolecular bonds present in the
polymer (hydrogen, dipole, Van der Waals, or ionic interactions with different values of dissociation
energy), as well as due to the different spatial arrangement of macromolecules, a specific
distribution of intermolecular bond strengths is observed between macromolecules of polymeric
materials, which match the Boltzmann distribution. However, radiation-induced (similarly as
temperature-induced) breaking of intermolecular bonds is not a random process subject to
Boltzmann’s distribution [24]. Since the failure of each bond leads to a redistribution of stresses in all
Figure 5. (a) Regression analysis of the functional dependence of the strength limit σm on the radiationdose; (b) Regression analysis of the functional dependence of the modulus M 40 on the radiation dose.
The realized regression analysis of the experimental data has shown that all the analyzedfunctional dependencies at a given interval of radiation dose can be described with a relativelyhigh degree of reliability by a single regression model, in the form
y(x) =N
∑i = 1
∆yi exp(∓
(xθi
)mi)
+ δ , (1)
where y(x) is the corresponding mechanical characteristic of the irradiated material, x is the radiationdose absorbed, and ∆yi, θi, mi, and δ represent unknown but the correct coefficients of the modelthat have been reliably estimated in the process of parametric fitting of experimental data using theTrust Region algorithm of non-linear least squares method [29] in the device ‘CF Tool’ of the Matlab®
software package. The following is then valid for the model coefficients ∆yi:
N
∑i = 1
∆yi = y(0) − δ, (2)
where y(0) is the initial value of the corresponding mechanical characteristic as it follows from therelation (1) for x = 0. The subscript i pertains to critical points of the curve y = y (x) where a significantchange in the velocity of its trend takes place, and N is the number of these critical points. The negativevalue of the quotient in the model exponent then represents a decreasing trend, while its positive value
Materials 2018, 11, 2405 10 of 13
represents the increasing trend of y(x). The coefficient δ represents a non-constant error parameter ofthe model, which will be discussed later.
The dashed lines in Figures 4 and 5 represent the 95% prediction intervals of the estimatedcoefficients of the model representing the 5% probability that the results of future measurements of themechanical characteristics of the irradiated PS PMX3 under the same experimental conditions will notlie between their lower and upper boundaries [30].
The regression model (1) describes changes in the observed mechanical characteristics of theirradiated polymeric material due to the prevalence of formation of transverse intermolecular bondsbetween macromolecular chains and their simultaneous breaking accompanied by degradationof the formed polymer network. Due to the different nature of intermolecular bonds presentin the polymer (hydrogen, dipole, Van der Waals, or ionic interactions with different values ofdissociation energy), as well as due to the different spatial arrangement of macromolecules, a specificdistribution of intermolecular bond strengths is observed between macromolecules of polymericmaterials, which match the Boltzmann distribution. However, radiation-induced (similarly astemperature-induced) breaking of intermolecular bonds is not a random process subject to Boltzmann’sdistribution [24]. Since the failure of each bond leads to a redistribution of stresses in all other bonds,each previous failure event has a notable effect on the failure of all remaining bonds. The interaction ofthese failures is therefore subject to Weibull’s statistics [31]. Given the above, the regression model(1) can be interpreted in a good approximation by the function of probability density of the Weibull’sdistribution of EB radiation-induced breaking of transverse intermolecular bonds of the irradiatedpolymer in the presence of simultaneous formation of a polymeric 3D network with new cross-links(quantified by an error δ of the model) in the following form [32]:
y(x) = bkxk−1e− bxk, (3)
where the pre-exponential factor or hazard function bkxk−1 of the Weibull’s distribution approximatesthe constants ∆yi, the scale parameter b = ±1/θi and the shape parameter, or the Weibull modulus k = mi.Since the sum (Σ∆yi + δ) approximates the initial values of the respective mechanical characteristics y(0)and θi of the radiation dose at the critical points of the curve y = y(x), the values ∆yi and θi depend onthe initial physical state of the irradiated sample of material, its properties and conditions of irradiation,while the Weibull’s moduli mi reflect the statistics of transverse intermolecular bonds breaking due toEB irradiation with different radiation doses. Since the breaking of bonds is conditioned by overcomingthe energy barrier of intermolecular forces, the values of the coefficients mi depend on the magnitudeof the activation energy of the individual relaxation events observed at the applied radiation dosesdue to the release of the polymeric chains with respect to the relevant type of motion corresponding tothe given primary as well as secondary relaxation event [33]. At the same time, the degree of chainsmobility is determined by the actual physical state of the polymer. In the glassy state, it is limited onlyto local movements of individual molecules, vibrations, bending and stretching of bonds, rotation oflateral molecular groups, and movement of only a few main chains. In the area of the glass transition,significant movement of lateral groups is possible, as well as gradual movement and reptation ofthe main chains, which transforms to a large-scale movement of segments and whole chains in arubbery state. The state of viscous flow allows for the sliding of whole macromolecular chains andglobal translations of entire polymer molecules between entanglements with subsequent decay ofthe polymeric material as a whole [34]. Since the critical condition for radiation-induced polymercross-linking is, in addition to the formation of secondary radicals in its amorphous regions, also thesufficiently high mobility of the chains which are carried by these secondary radicals, the radiationcross-linking by ionizing radiation is an optimal rubbery, or visco-elastic state with high mobility ofentire chains [28]. Since the sensitivity of the individual tensile characteristics εb, σb, σm, and M 40 tothe magnitude of the absorbed radiation dose is different, it can be naturally expected that values ofthe parameters mi for their description with the use of the model (1) will also be different.
Materials 2018, 11, 2405 11 of 13
The radiation cross-linking is an excessively-complicated process due to the complexity of thepolymerization reactions running in the irradiated three-component material, the analytical descriptionof which requires a solution of the system of non-linear differential equations. This solution can beobtained only with the use of numerical methods with an approximate result [34]. In order tosimplify this problem, the influence of the radiation-induced formation of the polymeric networkon the mechanical properties of the irradiated PS PMX3 in the model (1) is approximated only byan unknown, non-constant error parameter δ. The value of the error parameter at the same timedepends on the magnitude of the radiation dose x, as well as on the values of other coefficientsof the model ∆yi, θi, and mi, i.e., on the initial physical state of the irradiated material sample, itsproperties and conditions of irradiation, as well as on the activation energies of the relaxation eventsinitiated by individual radiation doses of the absorbed radiation that together determine the intensityof radiation-induced generation of cross-links and formation of polymer network.
The coefficients ∆yi, mi and δ, estimated in the process of parametric fitting of the experimentaldata, coefficients θi and percentage deviations of the coefficients ∆y(0) from their experimental values,as well as the statistical parameters ‘goodness of fit’ SSE, RMSE, R2 and Adj-R2 [35], are listed inTable 2 (for εb and σb) and Table 3 (for σm and M 40). Due to the aforementioned low number ofavailable experimental data, it was impossible to identify the coefficients θi by parametric fitting ofthe experimental data; therefore, they were estimated directly from the graphical interpretation of thefunctional dependencies of the monitored mechanical characteristics of the irradiated material.
Table 2. Results of the regression analysis of the functional dependence of εb and σb of the irradiatedmaterial on the magnitude of the radiation dose and statistical analysis of the quality of the foundregression model.
MechanicalCharacteristics θi ∆yi mi δ ∆y(0) (%) SSE R2 Adj-R2 RMSE
εb (%) 110 22.83 6.00350 0.5904 8.147 × 10−5 1 1 9.026 × 10−3
150 355.71 17.051
σb (MPa) 110 2.073 3.8252.2 2.319 4.877 × 10−6 1 1 1.562 × 10−3
150 8.147 × 10−5 1.053
Table 3. Results of the regression analysis of the functional dependence of σm and M 40 of irradiatedmaterial on the magnitude of the radiation dose and statistical analysis of the quality of the foundregression model.
MechanicalCharacteristics θi ∆yi mi δ ∆y(0) (%) SSE R2 Adj-R2 RMSE
σm (MPa)77 0.617 0.287
0.015 2.143 7.104 × 10−5 1 1 8.429 × 10−3138 0.045 15.261150 1.473 6.897
M 40 (MPa)77 0.272 0.321
1.591 2.708 3.737 × 10−4 0.9999 0.9998 3.67 × 10−3138 0.164 9.662150 0.091 16.761
Relatively low values of SSE and RMSE, the close proximity of the parameters R2 and Adj-R2 toone (or their equality at the value of one), and low values of deviations ∆y(0) show the relatively highperformance of the found model. However, due to the low amount of available experimental data,more detailed statistical analysis of the descriptive and predictive capabilities of the model was notpossible, and it will be necessary to realize this within the framework of ongoing research.
4. Conclusions
In this paper, for the first time, the effect of high-energy ionizing radiation on the mechanicalproperties of a melamine resin, phenol-formaldehyde resin, and nitrile rubber blend, commonly usedas a polymeric matrix of friction composite systems, especially in the automotive industry, was studied.
Materials 2018, 11, 2405 12 of 13
The study addressed the changes in the tensile characteristics of the respective blend after irradiationwith a 5 MeV electron beam, using the radiation doses ranging from 77 kGy to 284 kGy. The resultsof standard tensile tests have shown that irradiation with radiation doses up to 150 kGy inducedformation of a spatial polymeric network, and as a consequence, the values of stress at break,ultimate strength, and tensile modulus at strain of 40% significantly increase with the increasingdose of radiation until the value of strain at break of the irradiated blend decreases. At higher radiationdoses, the polymeric network formed as a result of irradiation already starts to degrade, and themonitored tensile characteristics of the blend are deteriorating. The radiation dose of 150 kGy thusappears to be optimal from the viewpoint of their significant improvement and the radiation treatmentof the given polymeric blend by the beam of accelerated electrons as a potential alternative to thetraditional chemical mode of treatment which burdens the environment.
The functional dependence of the monitored tensile characteristics on magnitude of the radiationdose with a value of up to 150 kGy was analyzed with a high degree of reliability by means of a new,physically-based model based upon the statistics of Weibull’s distribution of transverse intermolecularbonds of polymeric chains breaking under the influence of ionizing radiation with an error parameterquantifying the radiation-induced simultaneous formation of the polymeric network.
Author Contributions: I.K. developed the model and wrote the paper; I.L. and D.O. designed the experiments;J.V. (Juliana Vršková) and P.H. supervised all experiments and processed the experimental data; M.H. tested themodel and wrote the paper, J.V. (Jan Valícek) verified the model; M.K. performed verification of experimental data.
Funding: This research work has been supported by the Slovak Scientific Grant Agency project VEGA 1/0589/17,by the project “Center for Quality Testing and for Materials Diagnostics” ITMS code 26210120046 of the OperationalProgram Research and Development funded from European Fund of Regional Development, and by the researchand development project MSMT-15304/2017-1, the INTER-EXCELLENCE programme “European Anthroposphereas a Source of Raw Materials” LTC 17051.
Conflicts of Interest: The authors declare no conflict of interest
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